Chloro sulfone

Acetamidothiazole and its 4-alkyl derivatives react with chloro-sulfonic acid. The structure of the resulting products was a subject of controversy (172. 393-397). N-acetyl-A -(2-thiazolyl)-sulfamoyl chlorides (189) first proposed were then shown to be 2-acetamido-5-chloro-sulfonylthiazoles (190) (Scheme 120) (367. 368. 398). the latter assignment is based on infrared (368) and chemical evidence (367). 

Sulfonation with sulfur trioxide, pyridine sulfur trioxide, pyridine bis-sulfur trioxide, and dioxane sulfur trioxide, which are useful sul-fonating agents for acidophobic substances, have been applied to the thiophene seriesd At room temperature the 2-monosulfonic acid (isolated as the barium salt) is obtained in 86% yield. Higher temperatures lead to a disulfonic acid. However, sulfonation with chloro-sulfonic acid appears to be more convenient,as the sulfonyl chloride obtained can be used directly for the preparation of derivatives. 

The antiparasitic drug clorsulon (206), contains a rather unusual trichloroethylene group. This function is established early in the syntliesis by treatment of the perhalogenated compound 203 obtained from reduction of 202 with iron powder. Chlorosulfonation of 204 by means of chloro-sulfonic acid, followed by conver.sion of. sulfonyl chloride 205 to the amide, gives clorsulon (206) 153],... 

Treatment of a-chloro sulfones 250 with silver perchlorate in refluxing trifluoroacetic acid containing a small amount of water gives the corresponding aromatic ketones 251 in good yields (equation 150)143. 

NMR studies on graphite-phosphoric acid showed simultaneous, motional narrowing of both H and resonances above 225 K, indicating high mobility of phosphoric acid in the compound (FS). Chloro-sulfonic acid is inserted alone into graphite in the presence of many inorganic chlorides. The reaction temperature and stage seem to be related to the redox potential of the M"+-M couple (M3). 

Pandey et al. have used ultrasonic velocity measurement to study compatibility of EPDM and acrylonitrile-butadiene rubber (NBR) blends at various blend ratios and in the presence of compa-tibilizers, namely chloro-sulfonated polyethylene (CSM) and chlorinated polyethylene (CM) [22]. They used an ultrasonic interferometer to measure sound velocity in solutions of the mbbers and then-blends. A plot of ultrasonic velocity versus composition of the blends is given in Eigure 11.1. Whereas the solution of the neat blends exhibits a wavy curve (with rise and fall), the curves for blends with compatibihzers (CSM and CM) are hnear. They resemble the curves for free energy change versus composition, where sinusoidal curves in the middle represent immiscibility and upper and lower curves stand for miscibihty. Similar curves are obtained for solutions containing 2 and 5 wt% of the blends. These results were confirmed by measurements with atomic force microscopy (AEM) and dynamic mechanical analysis as shown in Eigures 11.2 and 11.3. Substantial earher work on binary and ternary blends, particularly using EPDM and nitrile mbber, has been reported. 

FIGURE 11,1 Ultrasonic velocity versus acrylonitrile-butadiene mbber/ethylene-propylene-diene monomer (NBR-EPDM) blend composition (a) no compatibiUzer, (b) with chloro-sulfonated polyethylene (CSM), and (c) with chlorinated polyethylene (CM). (From Pandey, K.N., Setua, D.K., and Mathur, G.N., Polym. Eng. Set, 45, 1265, 2005.)... 

When two polymers interact or react with each other, they are likely to provide a compatible, even a miscible, blend. Epoxidized natural rubber (ENR) interacts with chloro-sulfonated polyethylene (Hypalon) and polyvinyl chloride (PVC) forming partially miscible and miscible blends, respectively, due to the reaction between chlorosulfonic acid group and chlorine with epoxy group of ENR. Chiu et al. have studied the blends of chlorinated polyethylene (CR) with ENR at blend ratios of 75 25, 50 50, and 25 75, as well as pure rubbers using sulfur (Sg), 2-mercapto-benzothiazole, and 2-benzothiazole disulfide as vulcanizing agents [32]. They have studied Mooney viscosity, scorch... 

Sulfur trioxide reacts with MesSiCl 14 to give the trimethylsilyl ester of chloro-sulfonic acid 1334 [96], which on treatment vvdth iodosobenzene forms iodosoben-zenedichloride 1335, HMDSO 7, and regenerated SO3 [97]. Addition of olefins such as cyclohexene leads to the formation of sulfones such as 1336 [97]. With... 

Tibric acid (10), interestingly, has the m-carboxysulfonamido functionality but its activity is expressed, instead, as suppression of serum triglyceride levels. In its reported preparation, chloro-sulfonic acid treatment converts 2-chlorobenzoic acid to chlorosulfonate 9, which readily forms the hypolipidemic agent tibric acid (10) on reaction with... 

Thymidine has been selectively sulfated at HO-5 by using chloro-sulfonic acid in acetonitrile in the presence of pyridine.207... 

Chlorine trifluoride Chloro sulfonic acid Chromium trioxide (chromic acid)... 

Additional curing is often achieved with sulfur, peroxide, or maleimide formulations. Chloro-sulfonated polyethylene has improved resistance to oil, ozone, and heat compared to many other elastomers. Applications include harrier membranes and liners, surface coatings on fabrics, automobile air-conditioner hose, electrical cable insulation, and spark-plug boots [Andrews and Dawson, 1986],... 

The first studies on the sulfation of organic compounds, amino acids, and proteins have shown that pyridine/sulfur trioxide complex (pyridine/S03 or pyridine/Cl S03H),168-721 concentrated sulfuric acid,173,74 sulfuric acid//V,A -dicyclohexylcarbodiimide,175,761 and chloro-sulfonic acid177 are the most efficient reagents for the sulfation of tyrosine. More recently, alternative methods based on dimethylformamide/sulfur trioxide complex (DMF/S03),152,781 trimethylamine/sulfur trioxide (Me3N/S03),1152,1531 pyridinium acetylsulfate,137,791 and pyr-idinium trifluoroacetylsulfate1801 have been proposed to minimize side reactions which are difficult to control for the chemical sulfation of tyrosine peptides. 

Diphenyl-1,10-phenanthroline and 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline give disulfonic acids on reaction with chloro-sulfonic acid at 25°. The position of substitution was not established, but presumably it occurs in the two phenyl rings.281 An improved method of sulfonation utilizes hot fuming sulfuric acid.282... 

Examples are the sulfonating of polyethylene film with chloro-sulfonic acid (60) the sulfonating of sheets of phenolformaldehyde resin (77) the treatment of a film consisting of polystyrene and polyvinylchloride with concentrated sulfuric acid (4) the sulfonating of films consisting of aliphatic vinylpolymers with chlorosulfonic acid (125) the sulfonating of copolymers of a monovinyl- and a polyvinyl compound (30). Also are used copolymers of aromatic monovinyl-compounds and linear aliphatic polyene hydrocarbons (3) copolymers of an unsaturated aromatic compound and an unsaturated aliphatic compound (76), and of reaction products of poly olefines and partially polymerized styrene (173). 

These can be immobilized by either electrostatic adsorption on ion-exchangers [81] or sulfonated polystyrene [82], by hydrophobic interactions on organic polymers [83], by covalent binding to cellulose [68,84] and chloro-sulfonated polystyrene [71], or by entrapment in hydrogels [69,85]. Sol-gel based methods were established particularly for the preparation of fiber optic sensors [86-88]. 

S02C1 C1S020H + h2so4 chloro-sulfonation very vigorous... 

The alkyl sulfonyl chloride is usually synthesized using chloro-sulfonic acid... 

Chloro sulfonic acid asulam, bentazon, carbophenotion, chlorfenson, famphur, fiusulfamide, hexachlorobenzene, imazosulfuron, prosulfuron, tetradifon... 

The first step in the synthesis of saccharin is an electrophilic substitution reaction, like the first step of the benzocaine synthesis, but this time we want the orffio-substituted product. Chloro-sulfonic acid gives a mixture of ortho and para products—it is impossible to find conditions that completely avoid forming the pa ra-1 oluenes ulfonyl chloride. However, you may recognize an old friend here—the by-product is, of course, TsCl. You may have wondered why we always use TsCl and not PhS02Cl to make OH into a leaving group now you know. 

Sulfate diesters of chitin have been widely prepared because of their possible use as synthetic, blood anticoagulants. The sulfating reagent commonly used is chlorosulfonic acid in pyridine, but, more recently, chloro-sulfonic acid in 1,2-dichloroethane has been employed. Chitin disulfates can show up to 20 % of the anticoagulant potency of heparin, accompanied, in general, by only slight toxicity. ... 

Sulfonation or chlorosulfonation using fuming sulfuric acid or chloro-sulfonic acid are useful reactions. Sulfonations are often reversible and hence the sulfonate group may be used to protect a particular site on an aromatic ring. It can then be removed later in a synthetic sequence. 

A solution of 40 g. (0.37 mole) of anisole in 160 ml. of chloroform is cooled in an ice-salt bath to —8°, and 86.2 g. (0.74 mole) of chloro-sulfonic acid is added with stirring as rapidly as possible (about 20 minutes) while the temperature of the reaction mixture is maintained at 0 . Stirring is continued for 30 minutes while the temperature increases to room temperature. The mixture is poured into crushed ice and extracted with chloroform. The chloroform solution is washed with three small portions of ice water and is dried first over sodium sulfate and then over Drierite, and the solvent is removed under reduced pressure. Distillation of the residue gives a 66% yield of the sulfonyl chloride boiling at 103-105°/0.25 mm. (bath temperature 120-135°). The product melts at 41-42°. 

An alternative route to epoxides from ketones uses a-chloro sulfones and potas-... 

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